THERMOCHEMISTRY

Brown et. al., CHEM 120

Chapter 14 Background generated using:
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 Thermochemistry
The study of the energy changes that
occur during a chemical reaction
Energy – the capacity to do work or to transfer
heat
Work – the energy used to cause an object with
mass to move

Heat – the energy used to cause the

temperature of an object to rise

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 Energy
The capacity to do work or to transfer heat

Units:
1. SI unit – joules (J)

1 J = 1 kg m2 s-2

2. Old unit – calorie (cal)

1 cal = 4.184 J

3
 Law of Conservation of Energy
1st Law of Thermodynamics
Energy cannot be created nor destroyed in a
chemical reaction, but can be converted from one
form to another

Total Energy of the Universe is Constant

In a chemical reaction that generates heat:

Energy Lost by System = Energy Gained by Surroundings

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 Heat
Heat, q, is the form of energy in which thermal
energy is transferred from a hotter object to a
colder object.
-qSystem = +qSurroundings

The final temperatures of the objects will be equal.

The amount of heat, q, required to change the

temperature of a substance depends upon 3 factors:

1. The final temperature

2. Quantity of Substance (mass or moles)
3. Chemical Nature of the atoms/molecules
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 Heat Capacity
How much the temperature of a substance rises
when heat is absorbed depends upon the nature
and mass of the substance:
Heat Capacity, C – amount of energy required to raise
the temperature of a substance by 1 oC.
Units: J oC-1

Specific Heat Capacity, s – amount of energy required to

raise the temperature of 1 gram of a substance by 1 oC.
Units: J g-1 oC-1

Molar Heat Capacity – amount of energy required to raise

the temperature of 1 mole of a substance by 1 oC.
Units: J mol-1 oC-1
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 Determination of Heat Transferred
The amount of heat lost or gained by the system
is proportional to the change in temperature of
the system, ΔT:
Using:
Heat Capacity, C:
q = C x ΔT

Specific Heat Capacity,s:

q = m x s x ΔT

Molar Heat Capacity, MHC:

q = n x MHC x ΔT
Where
ΔT = TFinal – TInitial 7
Heat Capacity – Exercise 1

Question
Lead: 150 g at
100.0 °C;
Water: 50.0 g
at 22 °C; final
temperature
of mixture:
28.8 °C.
Calculate the
specific heat
of lead.

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 Heat Capacity – Exercise 1 soln.
Question
Calculate the specific heat of lead.

Solution
From the law of conservation of energy:
Heat given off by the Pb = Heat absorbed by the H2O
qlead = -qwater

First calculate the heat absorbed by the water:

qwater = m x s x ∆T
= 50.0 g x 4.184 J g-1 oC-1 x (28.8 – 22.0)
= 1.4 x 103 J
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 Heat Capacity – Exercise 1 soln.
The heat given off by the lead:
qlead = -qwater = -1.4 x 103 J

Calculate the specific heat capacity of the lead:

qlead = m x s x ∆T
where
∆T = Tfinal – Tinitial = 28.8 – 100.0 = -71.2 oC

.: rearrange and solve for specific heat of lead:

qlead -1.4 x 103 J

s= = = 0.13 J g-1 oC-1
m x ∆T 150.0 g x -71.2 oC
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 Heats of Reaction & Calorimetry
Chemical Energy – energy associated with
chemical bonds and intermolecular forces

Heat of Reaction, qRxn – amount of heat energy

transferred between system and surroundings
when a chemical reaction occurs at constant
temperature

E.g.: Combustion reaction, qCombustion

C2H5OH + O2(g) ➔ 2 CO2(g) + 6 H2O(g) + Energy

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 Exothermic & Endothermic
Regarding energy change, there are two types of
chemical reactions:

Exothermic Reaction – ΔE is negative

ie. energy is lost from the system to the surroundings
REACTANTS ➔ PRODUCTS + ENERGY

Endothermic Reaction – ΔE is positive

ie. energy is absorbed by the system from the
surroundings
REACTANTS + ENERGY ➔ PRODUCTS

Energy is given off in the form of heat, and measured as

a temperature change. 12
 Calorimeter
Apparatus for Measuring Heats of Reaction

Calorimetry – technique used to measure heat

exchange in chemical reactions
Heat lost by Rxn = Heat gained by
calorimeter & Water
qRxn = -(qcal + qwater)

qCal = Heat capacity x change in temperature

= C x ΔT

qWater = Mass x Specific Heat x Change in Temperature

= m x s x ΔT 13
Bomb Calorimeter

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 Calorimeter – Exercise 2
To calibrate a calorimeter, 3.000 kg of water was added
to the bomb, then a sufficient amount of a particular
compound was burned to produce 9.598 kJ of heat. The
temperature of the water was observed to rise by 0.629
C. The specific heat of water is 4.18 J g-1 °C-1 .

What is the heat capacity of the bomb?

HINT: Calculate:
1) qH2O 2) qCal 3) CCal
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 Calorimeter – Exercise 2 soln.
Calculate qWater:

qWater = m x s x ∆T
= 3000 g x 4.18 J g-1 oC-1 x 0.629 C
= 7.89 x 103 J
= 7.89 kJ
Calculate qcal:

Energy is produced and  qrxn is negative (exothermic)

i.e. qRxn = -[- (qCal + qWater)] = qCal + qWater

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 Calorimeter – Exercise 2 soln.
qCal = qRxn – qWater
= 9.598 kJ – 7.89 kJ
= 1.71 kJ

Using the equation:

qCal = C x ∆T
 rearrange and solve for C:

qCal 1.71 x 103 J

C= = = 2.72 x 103 J oC-1
∆T 0.629 oC
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 Heats of Reaction, ΔU & ΔH
With respect to chemical & physical processes:

Internal Energy, U – the energy of a compound

due its chemical bonds & intermolecular forces,
and kinetic energy

Enthalpy, H – heat absorbed or released in a

chemical reaction at constant pressure, .:
measure enthalpy change, ΔH

ΔHReaction = HProducts – HReactants

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 Enthalpy, H
Physical Processes:
Vaporisation: H2O(l) ➔ H2O(g) ΔHVap
Melting: H2O(s) ➔ H2O(l) ΔHMelting

(ΔH  strength of Intermolecular forces & BP)

Chemical Reactions:
Decomposition:
CaCO3 (s) ➔ CaO(s) + CO2(g) ΔHDecomp
Combustion:
CH4(g) + 2 O2(g) ➔ CO2(g) + 2 H2O(g) ΔHComb
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 Standard Enthalpy, Ho
Standard State refers to a Reaction performed
under standard conditions
Symbol: Ho Indicates std state
Standard enthalpy of Reaction, ΔHo – enthalpy change
for the reaction involving reactants in their standard
states, to products in their standard states at 25 oC.

Standard state conditions:

Temperature: 25 oC
Concentrations: 1 mol L-1
Pressures: 1 atm
Compounds: in the most stable phase for above
conditions
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 Hess’s Law – Indirect Method
“If a reaction is carried out in a series of steps,
H for the overall reaction will be equal to the
sum of the enthalpy changes for the individual
steps.”

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 Hess’s Law - Exercise 3
Using the data given, determine ΔHo for reaction
3 C(graphite) + 4 H2(g) ➔ C3H8(g)

C3H8(g) + 5O2(g) ➔ 3CO2(g) + 4H2O(l) ΔHo = -2219.9 kJ

C(graphite) + O2(g) ➔ CO2(g) ΔHo = -393.5 kJ
H2(g) + ½O2(g) ➔ H2O(l) ΔHo = -285.8 kJ

Solution:
1. Want C3H8 as a product .: reverse reaction 1:
3CO2(g) + 4H2O(l) ➔ C3H8(g) + 5O2(g) ΔHo = +2219.9 kJ
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 Hess’s Law - Exercise 3 cont.
2. Cancel out the CO2 .: multiply reaction 2 by 3:
3C(graphite) + 3O2(g) ➔ 3CO2(g) ΔHo = 3 x -393.5 kJ

3. Cancel out the H2O .: multiply reaction 3 by 4:

4H2(g) + 2O2(g) ➔ 4H2O(l) ΔHo = 4 x -285.8 kJ

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 Hess’s Law - Exercise 3 cont.
4. Add the reactions together and cancel to give overall
equation.
3CO2(g) + 4H2O(l) ➔ C3H8(g) + 5O2(g) ΔHo = +2219.9 kJ
3C(graphite) + 3O2(g) ➔ 3CO2(g) ΔHo = 3 x -393.5 kJ
4H2(g) + 2O2(g) ➔ 4H2O(l) ΔHo = 4 x -285.8 kJ
3 C(graphite) + 4 H2(g) ➔ C3H8(g)

5. Add the ΔHo’s together:

ΔHoRxn = (+2219.9) + (3 x -393.5) + (4 x -285.8)
= +2219.9 – 1181 – 1143

= – 104 kJ
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 Hess’s Law - Exercise 4
Calculate the standard enthalpy of formation of
CS2(l) given that:
C(graphite) + O2(g) ➔ CO2(g) ΔH0 = -393.5 kJ

S(rhombic) + O2(g) ➔ SO2(g) ΔH0 = -296.1 kJ

CS2(l) + 3 O2(g) ➔ CO2(g) + 2 SO2(g) ΔH0 = -1072 kJ

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 Hess’s Law - Exercise 4 soln.
Calculate the standard enthalpy of formation of
CS2(l) given that:
C(graphite) + O2(g) ➔ CO2(g) ΔH0 = -393.5 kJ

S(rhombic) + O2(g) ➔ SO2(g) ΔH0 = -296.1 kJ

CS2(l) + 3 O2(g) ➔ CO2(g) + 2 SO2(g) ΔH0 = -1072 kJ

Solution:
1. Write the enthalpy of formation reaction for CS2

C(graphite) + 2 S(rhombic) ➔ CS2(l)

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2. Add the given rxns so that the result is the desired rxn.
(molar ratios!)

C(graphite) + O2 (g) ➔ CO2(g) ΔH0 = -393.5 kJ

2S(rhombic) + 2O2 (g) ➔ 2SO2(g) ΔH0 = -296.1x2 kJ

+ CO2(g) + 2SO2 (g) ➔CS2 (l) + 3O2(g) ΔH0 = +1072 kJ

C(graphite) + 2 S(rhombic) ➔ CS2(l)

ΔH0 = -393.5 + (2 x -296.1) + 1072

= 86.3 kJ
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 Standard Enthalpy of Formation
ΔHof
The heat change when one mole of the
compound in its standard state, is formed from
its elements in their standard states at 25 oC.
E.g. Ethanol, C2H5OH(l)
Its elements: carbon, hydrogen & oxygen
Carbon: C(graphite)
Hydrogen: H2(g)
Oxygen: O2(g)

.: ΔHof of Ethanol, C2H5OH(l)

2C(graphite) + 3H2(g) + ½O2(g) ➔ C2H5OH(l) 28
 Standard Enthalpy of Formation
ΔHof
The standard enthalpy of formation of an
element in its standard state is taken to be
zero.

I.e.
ΔHof(C, graphite) = 0
ΔHof(H2, gas) = 0
ΔHof(O2, gas) = 0

BUT ΔHof(O3, gas) = 142.7 kJ mol-1

ΔHof(C, diamond) = 1.90 kJ mol-1
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 Standard Enthalpy of formation
Experimentally measured under standard
conditions (25 oC, 1 atm)

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 Calc of ∆H – Direct Method
The standard enthalpy of reaction (∆HoRxn) is
the enthalpy of a reaction carried out at 1 atm.

For the general reaction:

aA + bB ➔ cC + dD

The equation for the direct calculation of ∆HoRxn:

∆HoRxn = [d∆Hof(D) + c∆Hof(D)] - [a∆Hof(A) + b∆Hof(B)]

The general equation for the calculation of ∆HoRxn:

∆HoRxn = ∑m∆Hof(Products) - ∑n∆Hof(Reactants)

Where m & n are stoichiometric coefficients 31
Calc. of ∆H – Direct Method: Exercise 5
Given the standard enthalpies of formation of:
CO2(g) is –393.5 kJ mol-1; H2O(l) is –285.8 kJ mol-1 ;
and C2H6(g) is –84.7 kJ mol-1.
Calculate the standard enthalpy of combustion of
ethane.

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 Exercise 5 soln.
Given the standard enthalpies of formation of:
CO2(g) is –393.5 kJ mol-1; H2O(l) is –285.8 kJ mol-1 ;
and C2H6(g) is –84.7 kJ mol-1.
Calculate the standard enthalpy of combustion of
ethane.
C2H6(l) + 3½ O2(g) ➔ 2 CO2(g) + 3 H2O(l)

∆HoRxn = ∑m∆Hof(Products) - ∑n∆Hof(Reactants)

∆HoRxn = [2∆Hof(CO2, g) + 3∆Hof(H2O, l)] – [∆Hof(C2H6, l)]

Note: ∆Hof(O2, g) = 0 (by definition)

∆HoRxn = [(2 x – 393.5)+ (3 x – 285.8)] – [–84.7]

.: ∆HoRxn = – 1559.7 kJ mol-1 33